JP2001323066A - Cross-linking group-containing polyimide precursor, cross- linking group-containing polyimide, and heat-resistant adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To (1) provide a cross-linking group-containing polyamic acid that is a precursor of a cross-linking group-containing polyimide and has excellent storage stability, to (2) provide a cross-linked polyimide obtained by thermally treating the cross-linking group-containing polyimide that has excellent heat resistance and excellent soldering heat resistance, and to (3) provide a heat- resistant adhesive that contains (2) the cross-linked polyimide. SOLUTION: This cross-linking group-containing polyimide precursor characterized by having the cross-linking groups at 5 to 99 mol.% of the molecular terminals of repeating units represented by general formula (1) [L is a divalent bond of CO or C(CH3)2; M is a divalent bond of CO or C(CH3)2; Ar1 is tetravalent group of formula (V); X is a divalent group of formula (VI)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyimide precursor, a polyimide, and a heat-resistant adhesive. More specifically, a polyimide precursor having excellent storage stability, and
The present invention relates to a heat-resistant adhesive comprising polyimide having excellent solder heat resistance.

[0002]

2. Description of the Related Art Conventionally, a polyimide obtained by a reaction of a diamine and a tetracarboxylic dianhydride has excellent mechanical strength and dimensional stability in addition to its high heat resistance, flame retardancy, electric insulation and the like. Because of this, it is used in various fields such as electric and electronic equipment, aerospace equipment, and transportation equipment, and is expected to be widely used in fields requiring heat resistance in the future.

As heat-resistant adhesives, there have been known heat-resistant adhesives composed of many organic synthetic polymers. Among them, those having excellent heat resistance include polybenzimidazole-based and polyimide-based adhesives. Adhesives have been developed. Particularly, as a polyimide-based heat-resistant adhesive, an adhesive disclosed in U.S. Pat. No. 4,065,345, JP-A-61-134377, etc. is known as having excellent heat resistance and adhesive strength. ing. However, although these heat-resistant adhesives have excellent heat resistance and adhesiveness, high-temperature, high-pressure bonding conditions were required in order to obtain a good bonding state. Furthermore, the polyamic acid, which is a precursor of these heat-resistant adhesives, is liable to change with time, and the logarithmic viscosity and the solution viscosity gradually decrease with time even when stored at a low temperature under a nitrogen atmosphere. Therefore, it has been difficult to maintain the workability during coating and processing, the strength and adhesiveness of the resin itself after processing for a long period of time.

[0004] On the other hand, many methods have been reported for improving the adhesiveness by using a diaminosiloxane compound (Japanese Patent Application Laid-Open Nos. 5-72425 and 5-98233).
Nos. 5-98234, 5-98235, 5-
No. 98236, No. 5-98237, No. 5-11276
No. 0) has a problem in that the heat resistance inherent to the aromatic polyimide is impaired because the amount of the diaminosiloxane compound used in combination is large.

When polyimide is used as an adhesive for electronic materials, a metal laminate can be produced by thermocompression bonding using thermoplastic polyimide. However, when a thermoplastic polyimide is used, there is a problem that, for example, swelling occurs when the metal laminate is maintained at a temperature higher than the glass transition temperature of the resin after thermocompression bonding.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a crosslinking group-containing polyamic acid which is a precursor of a crosslinking group-containing polyimide and has excellent storage stability.

An object of the present invention is to provide a cross-linked polyimide obtained by heat-treating a cross-linking group-containing polyimide having excellent solder heat resistance.

One object of the present invention is to provide a heat-resistant adhesive containing a cross-linked polyimide obtained by heat-treating a cross-linked polyimide having excellent solder heat resistance.

[0009]

The heat-resistant adhesive described in the present invention is a dicarboxylic anhydride containing a cross-linking group having an unsaturated group at a part of molecular terminals, that is, a carbon-carbon double bond or a carbon-carbon triple bond. It is composed of a crosslinked group-containing polyimide or a crosslinked group-containing polyimide precursor which is a sealed linear polymer. The cross-linked polyimide is a polyimide obtained by thermally cross-linking a cross-linking group-containing polyimide.Since the unsaturated group introduced at the molecular end of the cross-linking group-containing polyimide becomes a cross-linking point by a thermal cross-linking reaction, The shape is a network polymer.

[0010] However, the crosslinked polyimide is completely different from the conventional thermosetting polyimide, and has a long distance between crosslink points, so that the crosslink density is low and the crosslinkable polyimide shows thermoplasticity before crosslink. That is, the cross-linked polyimide according to the present invention has thermoplasticity before cross-linking and has a film-forming ability, whereas the conventional bismaleimide-type thermosetting polyimide has a low molecular weight and thus is cross-linked. In the state before, there is no film forming ability, and it can be used only after curing.

According to the present invention, the crosslinkable polyimide having good heat resistance of the present invention has a thermally reactive crosslink point at the molecular terminal. It is an important feature that a crosslinked polyimide having excellent heat resistance can be obtained. Furthermore, by not completely sealing the amino group remaining at the molecular end with the cross-linking group-containing dicarboxylic anhydride and leaving a part of the amino group,
The storage stability of the cross-linking group-containing polyamic acid is better than the case where the polyamic acid is completely sealed. Another important feature is that the cross-linking group-containing polyimide obtained by imidizing the cross-linking group-containing polyamic acid and leaving a part of the amino groups at the molecular terminals does not easily swell during adhesion and solder heat resistance test.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have a specific repeating unit, and a part of the molecular terminal thereof has a carbon-carbon double bond or a carbon-carbon triple bond. Cross-linked polyimide obtained by heat-treating a cross-linking group-containing polyimide sealed with a cross-linking group-containing dicarboxylic anhydride or a cross-linking group-containing polyamic acid that is a precursor thereof has, in addition to the excellent physical properties inherent to the polyimide, Furthermore, they have found that they can be used as heat-resistant adhesives having excellent adhesiveness and storage stability and good solder heat resistance, and have reached the present invention. That is, the present invention is specified by the matters described in the following [1] to [11].

[1] A cross-linking group-containing polyimide precursor having a cross-linking group at 5 to 99 mol% of the molecular terminals of the repeating unit represented by the general formula (1) 1) In [Chemical formula 10], L represents -O-, -C (C
And a divalent group selected from the group consisting of H ₃ ) _2- . M
Is, -CO -, - indicating the selected from the group consisting of a divalent radical - C (CH _{3) 2.} Ar ₁ represents a tetravalent group selected from the group consisting of the formula (V) [Formula 11]. Formula (V) [Formula 1
In 1], X represents a divalent group selected from the group consisting of formula (VI) [Formula 11]. ).

[0014]

Embedded image

[0015]

Embedded image [2] 5 to 99 mol% of the molecular terminals are represented by the formula (I)
2] that 95 to 1 mol% of the molecular terminals are free of the cross-linking group represented by the formula (II) [formula 12]. The cross-linking group-containing polyimide precursor described in [1] (wherein Ar ₂ is represented by the formula (III) [Formula 1]
2] represents a divalent group selected from the group consisting of: Formula (I
II) In the formula, R _{1 to} R ₆ are each independently:
It may be the same or different and represents -H, -F, a trifluoromethyl group, a methyl group, an ethyl group, or a phenyl group. In the formula (III) [Formula 12], Y is a group represented by the formula (I)
V) represents a trivalent group selected from the group consisting of [Formula 12]. In the formula (IV), Z is a direct bond, -CO-,-
SO _2- , -S-, -O-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2-
Represents a divalent group selected from the group consisting of: ).

[0016]

Embedded image [3] a diamine represented by the general formula (3) [formula 13],
It is obtained by a polycondensation reaction of a tetracarboxylic dianhydride represented by the general formula (4) [Chemical formula 13] and a dicarboxylic anhydride containing a crosslinking group represented by the general formula (5) [Chemical formula 13]. The crosslinkable group-containing polyimide precursor described in [1] or [2] (where L is -O-, -C
And a divalent group selected from the group consisting of (CH ₃ ) ₂ —. M is, -CO -, - indicating the selected from the group consisting of a divalent radical - C (CH _{3) 2.} In the general formula (4),
Ar ₁ represents a tetravalent group selected from the group consisting of the formula (V) [Formula 14]. In the formula (V), X represents a divalent group selected from the group consisting of the formula (VI) [Formula 14]. In the general formula (5), Ar ₂ is a group represented by the formula (I)
II) represents a divalent group selected from the group consisting of [Formula 15]. In the formula (III), R _{1 to} R ₆ may be each independently the same or different;
—F, a trifluoromethyl group, a methyl group, an ethyl group, or a phenyl group. In the formula (III),
Is 3 selected from the group consisting of formula (IV) [Formula 15]
Shows a valence group. In the formula (IV), Z is a direct bond,
_{-CO -, - SO 2 -,} - S -, - O -, - C (CH 3) 2 -, - C
It represents a divalent group selected from the group consisting of (CF ₃ ) _2- . ).

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image [4] The crosslinkable group-containing polyimide precursor according to any one of [1] to [3], which has a logarithmic viscosity represented by Formula (A) [Formula 5] (In Formula (A),
[Η] is the logarithmic viscosity measured at 35 ° C. after dissolving the crosslinking group-containing polyimide precursor in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dl. ). [Equation 5] [η] = 0.2 to 2.0 dl / g (A) [5] The logarithmic viscosity retention R η calculated by Expression (B) [Equation 6] is calculated by Expression (C) [Equation 7]. Wherein the crosslinking group-containing polyimide precursor according to any one of [1] to [4] (where Rη is the logarithmic viscosity retention after storage, That is, 23 ° C
Is the retention of logarithmic viscosity after storage for 6 months. η [d
1 / g] is the logarithmic viscosity before storage, and η ′ [dl / g]
Is the logarithmic viscosity after storage at 23 ° C. for 6 months. ). [Equation 6] Rη [%] = η ′ [dl / g] ÷ η [dl / g] × 100 (B) [Equation 7] 90 [%] ≦ Rη [%] ≦ 100 [%] (C) [ 6] A cross-linking group-containing polyimide having a cross-linking group at 5 to 99 mol% of the molecular terminals of the repeating unit represented by the general formula (2) [Chem.
6], L represents a divalent group selected from the group consisting of —O— and —C (CH ₃ ) ₂ —. M is -CO-, -C (C
And a divalent group selected from the group consisting of H ₃ ) _2- . A
r ₁ represents a tetravalent group selected from the group consisting of formula (V) [Formula 17]. In the formula (V) [Formula 17], X represents the formula (V
I) a divalent group selected from the group consisting of: ).

[0020]

Embedded image

[0021]

Embedded image [7] 5 to 99 mol% of the molecular terminals are represented by the formula (VII)
The cross-linking group-containing molecular terminal represented by [Chemical Formula 18], and 95 to 1 mol% of the molecular terminal is represented by the formula (II)
8] The cross-linking group-containing polyimide according to [6] (wherein Ar ₂ is a compound represented by the formula (III) [ A divalent group selected from the group consisting of: embedded image wherein R _{1 to} R ₆ may be each independently the same or different; -H, -F, a trifluoromethyl group, a methyl group, an ethyl group, or a phenyl group, wherein Y is selected from the group consisting of the formula (IV) [Formula 18] In the formula (IV) [Formula 18], Z [Formula 18] is a direct bond, -CO-, -SO _2- , -S-, -O-, -C (CH ₃ ) ₂ -,-
It represents a divalent group selected from the group consisting of C (CF ₃ ) _2- . ).

Embedded image [8] The crosslinkable group-containing polyimide according to [6] or [7], wherein the polyimide has a logarithmic viscosity represented by Formula (D) [Formula 8] (in Formula (D), [η] is 0.5 g / d of a crosslinking group-containing polyimide was added to a phenol / p-chlorophenol mixed solution (10 parts by weight / 90 parts by weight)
logarithmic viscosity measured at 35 ° C. after dissolution at a concentration of 1). [Equation 8] [η] = 0.2 to 2.0 dl / g (D) [9] A crosslinked polyimide obtained by heat-treating the crosslinked group-containing polyimide according to [6] to [8],
When the crosslinked polyimide is used as a film (thickness: 4 μm) to form a laminate bonded to a copper foil (thickness: 18 μm), the laminated surface is immersed in a solder bath at 288 ° C. ± 5 ° C. for 10 seconds, and the bonding surface A cross-linked polyimide, wherein no peeling and / or swelling occurs.

[10] The crosslinked polyimide according to [9], wherein the heat treatment is performed at 250 to 450 ° C. for 0.1 second to 100 hours.

[11] A heat-resistant adhesive comprising the polyimide described in [6] to [10].

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the three kinds of polymers of a cross-linking group-containing polyimide, a cross-linking group-containing polyimide precursor, a polyimide, and / or a cross-linked polyimide obtained by heat-treating the polyimide precursor are collectively referred to as polyimide.

The diamine used to obtain the heat-resistant adhesive made of the polyimide is represented by the general formula (3). Specifically, 1,3-bis [4- (3-aminophenoxy) Benzoyl] benzene, 1,3-bis [4
-(4-aminophenoxy) benzoyl] benzene,
1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3
-Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy)
-Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α , Α-dimethylbenzyl] benzene and the like, but are not limited to these diamines.

In producing the polyimide according to the present invention, the following diamines may be mixed and polymerized within a range that does not impair these properties and physical properties. Examples of the diamine that can be used as a mixture include, for example,
m-phenylenediamine, o-phenylenediamine, p
Phenylenediamine, m-aminobenzylamine, o
-Aminobenzylamine, p-aminobenzylamine,
3-chloro-1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene, 2-methoxy-
1,4-phenylenediamine, 4-methoxy-1,2-
Phenylenediamine, 4-methoxy-1,3-phenylenediamine, 3,3′-dichlorobenzidine, 3,3 ′
-Dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,3 '
-Diamino-5,5'-ditrifluoromethyldiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,
4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4 ' -Dimethoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4-
(4-phenyl) phenoxybenzophenone, 3,3 ′
-Diamino-4,4'-di (4-phenylphenoxy)
Benzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl)-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-aminophenyl) -1,1,1,
3,3,3-hexafluoropropane, 3,3′-diaminodiphenylsulfoxide, 3,4′-diaminodiphenylsulfoxide, 4,4′-diaminodiphenylsulfoxide, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene,
1,4-bis (3-aminophenyl) benzene, 1,4
-Bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl)
Benzene, 1,3-bis (3-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyl sulfide) benzene, 1,3-bis ( 3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3-bis (3-aminobenzyl) benzene, 1, , 3-bis (4-aminobenzyl) benzene, 1,4-bis (4-aminobenzyl)
Benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-
α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene,
1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-aminophenoxy)
-4-trifluoromethylbenzene, 1,3-bis (3
-Aminophenoxy) -5-trifluoromethylbenzene, 1,3-bis (4-aminophenoxy) -4-trifluoromethylbenzene, 1,3-bis (4-aminophenoxy) -5-trifluoromethylbenzene, 1,4
-Bis (3-aminophenoxy) -3-trifluoromethylbenzene, 1,4-bis (4-aminophenoxy)
-5-trifluoromethylbenzene, 1,3-bis (3
-Amino-5-trifluoromethylphenoxy) benzene, 1,3-bis (3-amino-4-trifluoromethylphenoxy) benzene, 1,3-bis (4-amino-
2-trifluoromethylphenoxy) benzene, 1,3
-Bis (4-amino-3-trifluoromethylphenoxy) benzene, 1,4-bis (3-amino-5-trifluoromethylphenoxy) benzene, 1,4-bis (3
-Amino-4-trifluoromethylphenoxy) benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 1,4-bis (4-amino-
3-trifluoromethylphenoxy) benzene, 1,3
-Bis (3-amino-5-trifluoromethylphenoxy) -4-trifluoromethylbenzene, 1,3-bis (3-amino-5-trifluoromethylphenoxy)-
5-trifluoromethylbenzene, 1,3-bis (3-
Amino-4-trifluoromethylphenoxy) -4-trifluoromethylbenzene, 1,3-bis (3-amino-4-trifluoromethylphenoxy) -5-trifluoromethylbenzene, 1,3-[(3- Amino) -α,
α-bis (trifluoromethyl) benzyl] benzene,
1,3-[(4-amino) -α, α-bis (trifluoromethyl) benzyl] benzene, 1,4-[(3-amino) -α, α-bis (trifluoromethyl) benzyl]
Benzene, 1,4-[(4-amino) -α, α-bis (trifluoromethyl) benzyl] benzene, 1,3-
Bis (3-amino-4-fluorobenzoyl) benzene, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis [3-amino-4- (4
-Phenylphenoxybenzoyl] benzene, 2,6-
Bis (3-aminophenoxy) benzonitrile, 1,3
-Bis (4-aminophenoxy) -2-phenylbenzene, 1,3-bis [2- (3-aminophenyl) isopropyl] benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2-
(3-aminophenyl) isopropyl] benzene, 1,
4-bis [2- (4-aminophenyl) isopropyl]
Benzene, 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino) Phenoxy) phenyl] ketone, bis [4- (4-
Aminophenoxy) phenyl] ketone, bis [3- (3
-Aminophenoxy) phenyl] sulfide, bis [3
-(4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl ] Sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- ( 3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-
Aminophenoxy) phenyl] methane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane,
2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis [4- (3-aminophenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4′-bis (3-aminophenoxy) -3-
Methylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,
3 ', 5,5'-tetramethylbiphenyl, 4,4'-
Bis (3-aminophenoxy) -3,3'-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy)-
3,5-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy)
-3,3'-dibromobiphenyl, 4,4'-bis (3
-Aminophenoxy) -3,5-dibromobiphenyl,
4,4′-bis (3-aminophenoxy) -3,3 ′,
5,5′-tetrabromobiphenyl, 1,1-bis [4
-(3-aminophenoxy) phenyl] ethane, 1,1
-Bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane,
1,2-bis [4- (3-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-
Aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane,
2- [4- (4-aminophenoxy) phenyl] -2-
[4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4-
(4-aminophenoxy) phenyl] -2- [4- (4
-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy)
-3,5-dimethylphenyl] propane, 1,1-bis [4- (3-aminophenoxy) phenyl] butane,
1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,2-bis [4- (3-aminophenoxy) phenyl] butane, 1,2-bis [4- (4-aminophenoxy) Phenyl] butane, 1,3-bis [4-
(3-aminophenoxy) phenyl] butane, 1,3-
Bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (3-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4
-(4-aminophenoxy) phenyl] butane, 2,3
-Bis [4- (3-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, bis [4- (3-aminophenoxy)-
3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3, 5-dimethoxyphenyl] sulfide, bis [3- (3-aminophenoxy) phenyl] sulfoxide, bis [3- (4-aminophenoxy) phenyl] sulfoxide, bis [4-
(3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, 6,6′-bis (4-aminophenoxy) -3,
3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (3-aminophenoxy)-
3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4 -Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (phenoxy) phenoxy] diphenylsulfone and the like, and these diamines are used alone or in combination of two or more.

Further, part or all of the hydrogen atoms on the aromatic ring of the diamine is substituted with a substituent selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. Substituted diamines can be used. Further, an ethynyl group, a benzocyclobuten-4'-yl group, a vinyl group, an allyl group, a cyano group, an isocyanate group, a nitrile group, and an isopropenyl group which are cross-linking points are one of hydrogen atoms on the aromatic ring of the diamine. What introduced as a substituent in part or all can also be used. Further, a vinylene group, a vinylidene group, and an ethynylidene group, which are crosslinking points, may be incorporated in the main chain skeleton instead of the substituent.

The polyimide of the present invention can be copolymerized with one or more aliphatic diamines together with the above-mentioned diamines for the purpose of improving or modifying the performance. Specifically, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl)
Tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3
-Aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, 1,2-bis (aminomethoxy)
Ethane, bis [(2-aminomethoxy) ethyl] ether, 1,2-bis [(2-aminomethoxy) ethoxy]
Ethane, bis (2-aminoethyl) ether, 1,2-
Bis (2-aminoethoxy) ethane, bis [2- (2-
Aminoethoxy) ethyl] ether, bis [2- (2-
Aminoethoxy) ethoxy] ethane, bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, , 10-diaminodecane, 1,11-diaminoundecane, 1,12
-Diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,
6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.
2.1] heptane, and these diamines can be used alone or in combination of two or more.

The tetracarboxylic dianhydride used to obtain the polyimide according to the present invention is a tetracarboxylic dianhydride represented by the general formula (4).
Pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-
Benzophenonetetracarboxylic dianhydride, bis (3,
4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ) Methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4 -Bis (3,4-dicarboxyphenoxy)
Biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
Examples include 1,4,5,8-naphthalenetetracarboxylic dianhydride.

In producing the polyimide of the present invention, one or more of the following tetracarboxylic dianhydrides may be mixed and polymerized without impairing the properties and physical properties of the polyimide itself. Examples of the tetracarboxylic dianhydride that can be used as a mixture include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride,
Bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (2,3 -Dicarboxyphenyl)
Methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2-bis (2 , 3-Dicarboxyphenyl) ethane dianhydride,
1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxy) Phenoxy) benzene dianhydride, 1,2,5
6-naphthalenetetracarboxylic dianhydride, 1,2,2
3,4-benzenetetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, 2,
3,6,7-anthracenetetracarboxylic dianhydride,
1,2,7,8-phenanthrene tetracarboxylic dianhydride and the like, and these tetracarboxylic dianhydrides can be used alone or in combination of two or more.

Further, part or all of the hydrogen atoms on the aromatic ring of the tetracarboxylic dianhydride is selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group and a trifluoromethoxy group. Tetracarboxylic dianhydride substituted with the substituted substituent can be used. Further, an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group, a cyano group, which serves as a crosslinking point,
Those in which isocyanate groups, nitrilo groups, and isopropenyl groups have been introduced as substituents on some or all of the hydrogen atoms on the aromatic ring of the tetracarboxylic dianhydride can also be used. Further, a vinylene group, a vinylidene group, and an ethynylidene group, which are crosslinking points, may be incorporated in the main chain skeleton instead of the substituent.

The crosslinking group-containing dicarboxylic anhydride used to obtain the polyimide according to the present invention is a crosslinking group-containing dicarboxylic anhydride represented by the general formula (5). Specifically, maleic anhydride is used. Compound, 2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-fluoromaleic anhydride, 2,3-difluoromaleic anhydride, 2-trifluoromethylmaleic anhydride, 2, 3
-Ditrifluoromethylmaleic anhydride, 2-ethylmaleic anhydride, 2,3-diethylmaleic anhydride, 2-phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, 5-norbornene-2 , 3-Dicarboxylic anhydride, methyl-5-norbornene-2,3-
Dicarboxylic anhydride, dimethyl-5-norbornene-
2,3-dicarboxylic anhydride, fluoro-5-norbornene-2,3-dicarboxylic anhydride, difluoro-5-
Norbornene-2,3-dicarboxylic anhydride, trifluoromethyl-5-norbornene-2,3-dicarboxylic anhydride, ditrifluoromethyl-5-norbornene-
2,3-dicarboxylic anhydride, ethyl-5-norbornene-2,3-dicarboxylic anhydride, diethyl-5-norbornene-2,3-dicarboxylic anhydride, phenyl-5
-Norbornene-2,3-dicarboxylic anhydride, diphenyl-5-norbornene-2,3-dicarboxylic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride, 5-methyl-cis-1 , 2,3,4-tetrahydrophthalic anhydride, 5,6-dimethyl-cis-1,2,2
3,4-tetrahydrophthalic anhydride, 5-fluoro-
Cis-1,2,3,4-tetrahydrophthalic anhydride,
5,6-difluoro-cis-1,2,3,4-tetrahydrophthalic anhydride, 5-trifluoromethyl-cis-
1,2,3,4-tetrahydrophthalic anhydride, 5,6
-Ditrifluoromethyl-cis-1,2,3,4-tetrahydrophthalic anhydride, 5-ethyl-cis-1,2,2
3,4-tetrahydrophthalic anhydride, 5,6-diethyl-cis-1,2,3,4-tetrahydrophthalic anhydride, 1-phenyl-2- (3,4-dicarboxyphenyl) acetylene anhydride , 5-phenyl-cis-1,2,2
3,4-tetrahydrophthalic anhydride, 5,6-diphenyl-cis-1,2,3,4-tetrahydrophthalic anhydride, 6-ethynylphthalic anhydride, 1-phenyl-2
-(3- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride, 1-phenyl-2- (3-
(3,4-dicarboxyphenylcarbonyl) phenyl) acetylene anhydride, 1-phenyl-2- (3-
(3,4-dicarboxyphenylsulfonyl) phenyl) acetylene anhydride, 1-phenyl-2- (3-
(3,4-dicarboxyphenylsulfinyl) phenyl) acetylene anhydride, 1-phenyl-2- (3- (2
-(3,4-dicarboxyphenyl) isopropanyl)
Phenyl) acetylene anhydride, 1-phenyl-2- (3
-(1,1,1,3,3,3-hexafluoro-2-
(3,4-dicarboxyphenyl) isopropanyl) phenyl) acetylene anhydride, 1-phenyl-2- (3-
(3,4-dicarboxyphenyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenoxy) phenyl) acetylene anhydride
Phenyl-2- (4- (3,4-dicarboxyphenylcarbonyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (3,4-dicarboxyphenylsulfonyl) phenyl) acetylene anhydride, Phenyl-2
-(4- (3,4-dicarboxyphenylsulfinyl) phenyl) acetylene anhydride, 1-phenyl-2-
(4- (2- (3,4-dicarboxyphenyl) isopropanyl) phenyl) acetylene anhydride, 1-phenyl-2- (4- (1,1,1,3,3,3-hexafluoro-2- (3,4-dicarboxyphenyl) isopropanyl) phenyl) acetylene anhydride, 1-phenyl-2
-(4- (3,4-dicarboxyphenyl) phenyl)
Acetylene anhydride, 1-phenyl-2- (6- (2,3
-Dicarboxynaphthyl) acetylene anhydride,
These dicarboxylic anhydrides containing a crosslinking group may be used alone or in combination of two or more.

Further, part or all of the hydrogen atoms on the aromatic ring of the dicarboxylic anhydride having a crosslinking group may be selected from the group consisting of a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group and a trifluoromethoxy group. A crosslinking group-containing dicarboxylic anhydride substituted with a selected substituent can be used. Further, an ethynyl group, a benzocyclobuten-4′-yl group, a vinyl group, an allyl group,
Those in which a cyano group, an isocyanate group, a nitrilo group, and an isopropenyl group are introduced as a substituent into a part or all of the hydrogen atoms on the aromatic ring of the dicarboxylic anhydride containing the crosslinking group can also be used. Further, a vinylene group, a vinylidene group, and an ethynylidene group, which are crosslinking points, may be incorporated in the main chain skeleton instead of the substituent.

Among these dicarboxylic anhydrides containing a cross-linking group, maleic anhydride is most preferred from the viewpoints of performance and practical use of a polyimide from which maleic anhydride can be obtained.

In the present invention, the molecular weight is controlled by adjusting the molar ratio of the monomer components as in the case of the ordinary polycondensation polymer. That is, the tetracarboxylic dianhydride in the numerical range represented by the formula (E) (Equation 9) is used for the diamine. [Equation 9] M1: M2 = 1.00: 0.90 to 0.999 (E) [In the formula (E), M1 is the number of moles of diamine, M2
Indicates the number of moles of tetracarboxylic dianhydride.] When the amount of tetracarboxylic dianhydride relative to 1 mole of diamine is less than 0.9 mole, a molecular weight sufficient to bring out sufficient properties cannot be obtained, and when it exceeds 0.999 mole. Insufficient terminal sealing can be performed. Preferably, 0.92 to 0.99
9 mol, more preferably 0.95 to 0.999 mol, most preferably 0.96 to 0.999 mol.

An important feature of the present invention is the use of a dicarboxylic anhydride containing a crosslinking group. As a conventional technique, end capping is performed by using a terminal capping agent (total terminal capping agent amount) which is twice as much as the difference in the number of moles of diamine and tetracarboxylic dianhydride. 5 to 99 mol% of the total amount of the terminal blocking agent is sealed with a crosslinking group-containing dicarboxylic anhydride, that is, 95 to 1 mol% of the total amount of the terminal blocking agent.
Means that the amino group remains. When a crosslinking group-containing dicarboxylic anhydride having a numerical value larger than the numerical range is used, the storage stability of the polyimide precursor solution is poor, and a decrease in the molecular weight is observed during storage at room temperature (23 ° C.). As an index of storage stability, there is a retention rate of logarithmic viscosity, and specifically, a logarithmic viscosity retention rate Rη calculated by Expression (B) [Equation 10] is:
That is, the numerical value range is represented by Expression (C) [Equation 11]. [Equation 10] Rη [%] = η ′ [dl / g] ÷ η [dl / g] × 100 (B) [In the formula (B), Rη is the logarithmic viscosity retention after storage, that is, at 23 ° C. The logarithmic viscosity retention after storage for 6 months. η [dl / g] is the logarithmic viscosity before storage, and η '[dl / g] is the logarithmic viscosity after storage at 23 ° C for 6 months. [Equation 11] 90 [%] ≦ Rη [%] ≦ 100 [%] (C) A soldering heat test is performed as a method for evaluating heat resistance.
After drying at 135 ± 10 ° C. for 60 minutes, the state after being immersed in a solder bath at 288 ± 5 ° C. for 10 seconds was visually evaluated to determine whether peeling and / or swelling occurred on the bonding surface.

When an excessive amount of the dicarboxylic anhydride containing a crosslinking group is present, a decomposition reaction of the unreacted dicarboxylic anhydride containing a crosslinking group occurs during the heat treatment and the soldering heat test,
It causes peeling and swelling. In addition, if it is less than the numerical value range, sufficient terminal sealing cannot be performed. The preferred amount of the dicarboxylic anhydride containing a crosslinking group is 10% of the total amount of the terminal blocking agent.
~ 99 mol%, more preferably 20 ~ 99 mol%
And most preferably 50 to 99 mol%.

In producing the polyimide according to the present invention, one or more of the following dicarboxylic anhydrides may be mixed and polymerized without impairing the properties and physical properties of the polyimide itself. Dicarboxylic anhydrides that can be used as a mixture include phthalic anhydride, 3
-Fluorophthalic anhydride, 4-fluorophthalic anhydride,
3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 3
-Bromophthalic anhydride, 4-bromophthalic anhydride, 3-
Nitro phthalic anhydride, 4-nitro phthalic anhydride, 3-cyano phthalic anhydride, 4-cyano phthalic anhydride, 3-methyl phthalic anhydride, 4-methyl phthalic anhydride, 3-methoxy phthalic anhydride, 4-methoxy Phthalic anhydride, 3-trifluoromethyl phthalic anhydride, 4-trifluoromethyl phthalic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-
Diphenyl ether dicarboxylic anhydride, 2,3-diphenyl ether dicarboxylic anhydride, 3,4-diphenyl sulfide dicarboxylic anhydride, 2,3-diphenyl sulfide dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2, 3-benzophenone dicarboxylic anhydride, 3,4-diphenylsulfone dicarboxylic anhydride, 2,3-diphenylsulfone dicarboxylic anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3
-Naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride and the like, and also contains an ethynyl group represented by ethynylphthalic anhydride and 6-ethynyl-2,3-dicarboxynaphthalene anhydride. A dicarboxylic anhydride and a benzocyclobuten-4′-yl group,
A phthalic anhydride derivative or a 2,3-dicarboxynaphthalene anhydride derivative containing a vinyl group, an allyl group and an isopropenyl group may be used alone or in combination of two or more with the above-mentioned dicarboxylic anhydride containing a crosslinking group. it can.

The method for producing a polyimide according to the present invention can be applied to all methods including known methods capable of producing a polyimide, but it is particularly preferable to carry out the reaction in an organic solvent. Examples of usable organic solvents include, for example, phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol -
2,5-xylenol, 2,6-xylenol, 3,4
-Xylenol, 3,5-xylenol, N, N-dimethylformamide, N, N-dimethylacetamide,
N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,
3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2 -Methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-
Examples thereof include dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, and anisole. These organic solvents can be used alone or
A mixture of more than one species may be used.

Further, there is no problem even if the following solvents coexist. Examples of organic solvents that can coexist include benzene, toluene, o-xylene, m-xylene, p-xylene, o-chlorotoluene, m-chlorotoluene and p-toluene.
-Chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, chlorobenzene, bromobenzene and the like.

In the production of the polyimide according to the present invention, the method of adding and reacting a diamine, a tetracarboxylic dianhydride and a dicarboxylic anhydride containing a cross-linking group in an organic solvent is as follows. A method in which the reaction is continued by adding a dicarboxylic anhydride containing a crosslinking group after the reaction of the acid dianhydride component, and (b) adding a diamine and a dicarboxylic anhydride containing a crosslinking group to cause a reaction, and then adding tetracarboxylic acid. A method in which a dianhydride component is added and the reaction is further continued; and (c) a method in which a diamine, a tetracarboxylic dianhydride, and a dicarboxylic anhydride having a crosslinking group are simultaneously added and reacted, and the like. Can be taken.

In producing the cross-linking group-containing polyimide or the cross-linking group-containing polyimide precursor, first, the cross-linking group-containing polyimide precursor is cooled to a low temperature of 100 ° C. or less, specifically, −2
The synthesis is carried out at 0 to 70 ° C, preferably at 0 to 60 ° C.
By raising the temperature to 50 to 300 ° C. and imidizing, a polyimide containing a crosslinking group can be obtained (thermal imidization). In addition, imidation is a method of chemically imidizing using an imidizing agent such as acetic anhydride (chemical imidization), or after mixing a diamine, a tetracarboxylic dianhydride and a dicarboxylic anhydride containing a crosslinking group. , An organic base and / or
Alternatively, imidization can also be carried out by immediately raising the temperature in the presence or absence of an azeotropic dehydration solvent (direct thermal imidization).

The reaction time depends on the type of monomer used, type of solvent, type of organic base catalyst, type of azeotropic dehydration solvent,
Although it depends on the amount and the reaction temperature, as a guide, 1-4
8 hours, usually several hours to over a dozen hours. When performing direct thermal imidization, as a guide, the reaction proceeds until the amount of distilled water reaches almost the theoretical amount (usually, not all of the water is recovered, so the recovery is 70 to 90%). It is usually several hours to several tens of hours. In this case, a method in which water generated by imidization is removed with an azeotropic agent such as toluene is general and effective.

The reaction pressure is not particularly limited, but usually atmospheric pressure is sufficient. The reaction atmosphere is not particularly limited, but is usually air, nitrogen, helium, neon, or argon, and preferably nitrogen or argon which is an inert gas.

When a polymerization reaction is carried out in an organic solvent to produce a polyimide containing a crosslinking group, an organic base catalyst is preferably used. As the organic base catalyst, for example,
Triethylamine, tributylamine, tripentylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, α-picoline, β-picoline, γ-
Examples include picoline, 2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, etc., preferably pyridine and γ-picoline. The use amount of these catalysts is not particularly limited as long as the polymerization reaction rate is substantially improved.

The amount of the organic base to be used is represented by the formula (F) [Equation 1]
2]. [Equation 12] M1: M4 = 1: 0.001 to 1: 0.500 (F) [In the formula (F), M1 is the same as above, and M4
Is the number of moles of the organic base catalyst. In the present invention, the logarithmic viscosity of the crosslinking group-containing polyimide precursor is in the numerical range of the mathematical formula (A) [Equation 13]. [Equation 13] [η] = 0.2 to 2.0 dl / g (A) [In the formula (A), [η] represents 0.5 g of a crosslinking group-containing polyimide precursor in N-methyl-2-pyrrolidone. / D
Logarithmic viscosity measured at 35 ° C. after dissolution at a concentration of 1. The logarithmic viscosity of the cross-linking group-containing polyimide is represented by the formula (B)
This is the numerical range of [Equation 14]. [Equation 14] [η] = 0.2 to 2.0 dl / g (B) [In the formula (B), [η] is a cross-linked group-containing polyimide mixed with a phenol / p-chlorophenol mixed solution (10
/ 90 [wt / wt]) at a concentration of 0.5 g / dl and then logarithmic viscosity measured at 35 ° C].

The method of bonding using the heat-resistant adhesive of the present invention includes the steps of: a) casting a cross-linking group-containing polyimide precursor solution, a cross-linking group-containing polyimide solution or a suspension thereof on an adherend; Alternatively, after applying, heat and dry. Furthermore, bonding is performed by heating and pressing the other adherend and the polyimide surface together.

B) On one or both sides of a sheet having heat resistance, a cross-linking group-containing polyimide precursor solution, a cross-linking group-containing polyimide solution or a suspension thereof is cast or coated on an adherend, and then heated. dry. The sheet having the adhesive layer and the adherend are bonded together by heating and pressing.

C) A polyimide film containing a cross-linking group is prepared by applying the cross-linking group-containing polyimide precursor solution to a glass plate or the like, followed by drying. After the polyimide film is peeled off from a glass plate or the like, bonding is performed by heating and pressing together with the adherend.

D) A crosslinked group-containing polyimide is kneaded and extruded to produce an extruded film. The film is bonded to the adherend by heating and pressing to adhere. And the like, but the bonding is not limited to the above-mentioned method.

The crosslinked polyimide according to the present invention is obtained by heat-treating a crosslinkable polyimide containing a crosslinkable group. The `` heat treatment '' in the present invention means that, due to a chemical reaction, a carbon-carbon triple bond in a crosslinking group-containing dicarboxylic anhydride introduced into a molecular terminal thermally reacts to form a bridge between molecular chains. means. The temperature, time, pressure and method of the heat treatment are not particularly limited, but are shown below as typical examples.

The heat treatment temperature is generally about 250 to 450 ° C., preferably about 300 to 400 ° C., and most preferably about 330 to 380 ° C. in practical terms. In general, at a temperature lower than 250 ° C., a crosslinking reaction hardly occurs, and at a temperature higher than 450 ° C., the cross-linked polyimide tends to be denatured, and it is difficult to sufficiently obtain its properties.

The heat treatment time varies depending on other heat treatment conditions, but is usually preferably 0.1 second to 100 hours, preferably about 1 second to 30 hours, and most preferably about 10 seconds to 10 hours. If the heat treatment time is shorter than 0.1 second, the cross-linking reaction is not sufficient, and if it is longer than 100 hours, the cross-linked polyimide is liable to be modified, and its properties are hardly obtained.

The pressure of the heat treatment is usually sufficient at atmospheric pressure, but the heat treatment can be performed under pressure. The heat treatment atmosphere is not particularly limited, but is usually air, nitrogen, helium, neon, or argon, and preferably nitrogen or argon which is an inert gas.

Further, a metal catalyst containing gallium, germanium, indium, and lead, molybdenum, manganese, nickel, cadmium is used for the purpose of controlling the reaction rate by accelerating or suppressing the cross-linking reaction progressed by the heat treatment. , Cobalt, chromium, iron, copper, tin, platinum and the like, and a phosphorus compound, a silicon compound, a nitrogen compound and a sulfur compound. For the same purpose, irradiation with radiation such as infrared rays, ultraviolet rays, α, β, and γ rays, electron beams, and X-rays, as well as plasma treatment and doping treatment can be performed.

The heat treatment method is not limited by the form of the crosslinking group-containing polyimide. That is, specific examples of the heat treatment method include, for example, a method of heat-treating a cross-linking group-containing polyimide obtained as a film, a powder, or a granule by the following methods.

A method of performing heat treatment as it is. This method, because the cross-linked polyimide can be obtained in the form of powder or granules,
It can be added to other resins as a filler as it is, or applied to molded products by sinter molding.

[0058] A method in which once a melt-forming process is performed to obtain a molded product having a desired shape, the molded product is heat-treated. This method can be applied to general melt molding.

A method of performing a heat treatment at the same time as performing a melt forming process. This method can be applied particularly to molding of a film or sheet by pressing, and utilization as an adhesive.

A method in which the heat treatment is carried out halfway as it is, then subjected to a melt forming process once to obtain a molded product having a desired shape, and then heat-treating the molded product again. This method can be applied to general melt molding processing in general, molding of films and sheets by pressing, and use as an adhesive.

The solution or suspension obtained from the polyimide according to the present invention is important in the pretreatment step for processing the polyimide containing a crosslinking group according to the present invention. The solution or suspension can be prepared by using a solvent that does not cause a chemical reaction with the crosslinking group-containing polyimide of the present invention. Solvents that can be used include the solvents described above. These solvents can be used alone or in combination of two or more. When used as a mixture, it is not always necessary to select a combination of solvents that dissolve each other at an arbitrary ratio, and a non-uniform state in which the solvents cannot be mixed uniformly may be used. The concentration of the solution or suspension containing the polyimide according to the present invention is not limited.

The concentrations are defined as percentages of the total weight of the used polyimide of the present invention with respect to the total weight of all the solvents used and the polyimide of the present invention. The concentration can be applied in the range of 1 to 60%,
Preferably it is in the range of 5 to 40%, more preferably 10 to 30%. The method for preparing the solution or suspension containing the polyimide of the present invention is not limited, and all known methods can be applied.

[0063] Among the heat-resistant adhesives of the present invention, the polyimide containing a crosslinking group can be melt-molded. Melt processing is to heat the cross-linking group-containing polyimide to a molten state,
This is a process of performing various shaping in that state, and includes all molding using a molten state. The applicable molding methods are
Extrusion molding, injection molding, compression molding, sinter molding, blow molding, vacuum molding, rotational molding, powder molding, reaction injection molding,
It is a lamination molding and casting type.

The heat-resistant adhesive of the present invention may contain a thermoplastic resin, for example, polyethylene, within the range not impairing the object of the present invention.
Polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polystyrene, polyvinyl acetate,
ABS resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polycarbonate, PTFE, celluloid, polyarylate, polyether nitrile, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenylene sulfide, polyamide imide, polyether imide, modified polyphenylene Oxides and polyimides, or thermosetting resins, such as thermosetting polybutadiene, formaldehyde resin, amino resin, polyurethane, silicone resin, SBR, NBR, unsaturated polyester, epoxy resin, polycyanate, phenolic resin and polybismaleimide It is also possible to blend or alloy one or more resins in an appropriate amount depending on the conditions. The method is not particularly limited, and a known method can be applied.

The heat-resistant adhesive of the present invention may be mixed with various fillers or additives as long as the object of the present invention is not impaired. Examples thereof include abrasion resistance improvers such as graphite, carborundum, silica stone powder, molybdenum disulfide, and fluororesin, flame retardant improvers such as antimony trioxide, magnesium carbonate, and calcium carbonate, clay, and mica. Electric property improver such as, asbestos, silica, tracking resistance improver such as graphite, barium sulfate, silica, acid resistance improver such as calcium metasilicate, iron powder,
Thermal conductivity improvers such as zinc powder, aluminum powder and copper powder, and other glass beads, glass spheres, talc, diatomaceous earth, alumina, silica balun, hydrated alumina, metal oxides, coloring agents and pigments. The mixing method is not particularly limited, and a known method can be applied.

[0066]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, various physical properties were measured by the following methods.

Logarithmic viscosity: A value measured at 35 ° C. after dissolving the polyimide precursor in N-methyl-2-pyrrolidone at a concentration of 0.50 g / 100 ml.

Adhesive strength: IPC-TM650met
The value measured by a 90 ° peel test according to hod 2, 4, and 9.

Solder heat resistance test: 60 at 135 ± 10 ° C.
After being dried for a minute, the state when immersed in a solder bath at 288 ± 5 ° C. for 10 seconds was visually judged.

Example 1 [Polymerization of Polyamic Acid Solution] 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene 105 was stirred and placed in a vessel equipped with a nitrogen inlet tube. .
748 g (0.200 mol) and 379.93 g of N-methyl-2-pyrrolidone were charged and stirred for 30 minutes under a nitrogen atmosphere. Thereafter, 57.0787 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
(0.194 mol) was added in portions, paying attention to the solution temperature, and the mixture was stirred at room temperature for 6 hours. Next, 1.1375 g (0.0116 mol) of maleic anhydride was added, followed by another 10 minutes.
Stirred for hours. The logarithmic viscosity of the polyamic acid solution thus obtained was 0.78 dl / g.

[Preparation of Polyimide Adhesive Film] A part of the polyamic acid solution was taken and used as a base film.
uPont non-thermoplastic polyimide film Kapt
After casting on on-ENZT, 100 ° C, 200
It heated for 1 hour at 250 degreeC and 250 degreeC, respectively, and produced the polyimide adhesive film.

[Preparation of Crosslinked Polyimide Laminate] The above polyimide adhesive film (4 μm) was rolled with a rolled copper foil BHY-02BT (18 μm) manufactured by Japan Energy Co., Ltd.
After thermocompression bonding under the conditions of 5 kg / cm ² and a temperature of 280 ° C. for 1 hour to form a crosslinked group-containing polyimide laminate comprising an adhesive sheet layer / copper foil layer, it is further subjected to 360 ° in an autoclave.
A heat treatment was performed at 4 ° C. for 4 hours to obtain a crosslinked polyimide laminate.

[Adhesion Test] Using the obtained crosslinked polyimide laminate, IPC-TM650method2,4,4
9. As a result of performing a 90 ° peel test in accordance with No. 9, 2.39 kg
/ Cm.

[Storage Stability Test] After the polyamic acid solution was purged with nitrogen and stored at 23 ° C. for 6 months, the logarithmic viscosity was 0.77 dl / g, and the retention of logarithmic viscosity was 99%. Further, after forming a crosslinked polyimide laminate in the same manner as before storage, an adhesion test was performed, and the adhesion strength was 2.3.
It was 7 kg / cm.

[Solder Heat Resistance Test] The crosslinked polyimide laminate was dried at 135 ° C. for 60 minutes, and then immersed in a solder bath at 288 ° C. with the copper foil face down for 10 seconds. Was not seen at all and was good.

Examples 2 to 12 Synthesis of polyamic acid and various tests in the same manner as in Example 1 except that the types and amounts of the tetracarboxylic dianhydride and the terminal blocking agent were changed to those shown in Table 1. Example 1
The results are shown in Table 3 together with

Comparative Examples 1 to 4 Synthesis of polyamic acid and various tests in the same manner as in Example 1 except that the types and amounts of tetracarboxylic dianhydride and terminal blocking agent were changed to those shown in Table 2. Example 1
The results are shown in Table 4.

As shown in Tables 1 and 3, when the proportion and / or logarithmic viscosity of the diamine, tetracarboxylic dianhydride and terminal capping agent were within the range of the present invention, the storage stability of the polyamic acid precursor was determined. Is good, and the adhesive strength and solder heat resistance are good.

On the other hand, as shown in Tables 2 and 4, when the proportion and / or logarithmic viscosity of the diamine, tetracarboxylic dianhydride and terminal capping agent is out of the range of the present invention, the polyamic acid precursor It can be seen that the storage stability of the body is poor, and the adhesive strength and solder heat resistance are both poor.

[0080]

According to the present invention, a crosslinkable group-containing polyamic acid which is a precursor of a crosslinkable group-containing polyimide and has excellent storage stability can be provided.

According to the present invention, there can be provided a crosslinked polyimide obtained by heat-treating a crosslinked group-containing polyimide which is excellent not only in heat resistance but also in solder heat resistance.

According to the present invention, it is possible to provide a heat-resistant adhesive containing a cross-linked polyimide obtained by heat-treating a cross-linkable group-containing polyimide having not only heat resistance but also excellent solder heat resistance.

[0083]

[Table 1]

[0084]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB17B AB33B AK49A BA02 BA07 GB43 JB12A JJ03 4J040 EH031 LA05 LA08 MA02 NA19 4J043 PA02 PB03 QB31 RA05 SA06 TA22 TA23 UA122 UA132 UA142 UA152 UB121 UB121 UB121 UB151 ZB01

Claims (11)

[Claims] 1. A cross-linking group-containing polyimide precursor having a cross-linking group at 5 to 99 mol% of the molecular terminals of the repeating unit represented by the general formula (1) In Formula 1, L represents a divalent group selected from the group consisting of —O— and —C (CH ₃ ) ₂ —.
And a divalent group selected from the group consisting of -C (CH ₃ ) _2- . Ar ₁ represents a tetravalent group selected from the group consisting of the formula (V) [Formula 2]. In the formula (V) [Formula 2], X is
A divalent group selected from the group consisting of the formula (VI) [Formula 2] is shown. ). Embedded image Embedded image 2. The compound of the formula (I) wherein 5-99 mol% of the molecular terminal is
The cross-linking group-containing molecular terminal represented by [Chemical Formula 3], and 95 to 1 mol% of the molecular terminal is represented by the formula (II)
The cross-linking group-containing polyimide precursor according to claim 1, wherein Ar ₂ is a compound represented by the formula (III) [ A divalent group selected from the group consisting of:
II) In the chemical formula 3, R _{1 to} R ₆ are each independently the same or different, and may be -H, -F, a trifluoromethyl group, a methyl group, an ethyl group, or Indicates a phenyl group. In the formula (III) [formula 3], Y is a group represented by the formula (IV)
A trivalent group selected from the group consisting of [Chemical Formula 3] is shown. In formula (IV) [formula 3], Z [formula 3] is a direct bond, -CO-,-
SO _2- , -S-, -O-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2-
Represents a divalent group selected from the group consisting of: ). Embedded image 3. A diamine represented by the general formula (3) [Formula 4], a tetracarboxylic dianhydride represented by the general formula (4) [Formula 4], and a general formula (5) [Formula 4] The crosslinkable group-containing polyimide precursor according to claim 1 or 2, which is obtained by a polycondensation reaction of the crosslinkable group-containing dicarboxylic anhydride represented by the general formula (3), wherein L is- O-, -C (C
And a divalent group selected from the group consisting of H ₃ ) _2- . M
Is, -CO -, - indicating the selected from the group consisting of a divalent radical - C (CH _{3) 2.} In the general formula (4),
₁ represents a tetravalent group selected from the group consisting of the formula (V) [Formula 5]. In the formula (V) [Formula 5], X is a group represented by the formula (VI)
It represents a divalent group selected from the group consisting of [Formula 5]. In the general formula (5), Ar ₂ represents a divalent group selected from the group consisting of the formula (III) [Formula 6]. Formula (I
II) In Chemical Formula ₆ , R _{1 to} R ₆ are each independently the same or different, and are each —H, —F, a trifluoromethyl group, a methyl group, an ethyl group, or Indicates a phenyl group. In the formula (III) [Formula 6], Y is a group represented by the formula (IV)
It represents a trivalent group selected from the group consisting of [Formula 6]. In the formula (IV) [Formula 6], Z is a direct bond, -CO-, -SO ₂ -,-
S -, - O -, - C (CH 3) 2 -, - indicating the selected from the group consisting been bivalent radical - C (CF _{3) 2.} ). Embedded image Embedded image Embedded image 4. The crosslinked group-containing polyimide precursor according to any one of claims 1 to 3, wherein the polyimide precursor has a logarithmic viscosity represented by Formula (A) [Formula 1]. [Η] is the logarithmic viscosity measured at 35 ° C. after dissolving the crosslinking group-containing polyimide precursor in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dl.) [Equation 1] [η] = 0.2 to 2.0 dl / g (A) 5. The logarithmic viscosity retention Rη calculated by the formula (B) [Equation 2] is within a numerical range represented by the formula (C) [Equation 3]. 4. In the crosslinkable group-containing polyimide precursor described in any one of (4) and (wherein Rη is the logarithmic viscosity retention after storage, ie, 23
The retention of logarithmic viscosity after storage at 6 ° C. for 6 months. η
[Dl / g] is the logarithmic viscosity before storage, and η '[dl /
g] is the logarithmic viscosity after storage at 23 ° C. for 6 months. ). [Equation 2] Rη [%] = η ′ [dl / g] ÷ η [dl / g] × 100 (B) [Equation 3] 90 [%] ≦ Rη [%] ≦ 100 [%] (C) 6. A cross-linking group-containing polyimide having a cross-linking group at 5 to 99 mol% of the molecular terminal of the repeating unit represented by the general formula (2) (formula (2))
[Chemical Formula 7] in, L is, -O -, - indicating the selected from the group consisting of a divalent radical - C (CH _{3) 2.} M is -CO-, -C
And a divalent group selected from the group consisting of (CH ₃ ) ₂ —. Ar ₁ represents a tetravalent group selected from the group consisting of the formula (V) [Formula 8]. In the formula (V) [Formula 8], X represents a divalent group selected from the group consisting of the formula (VI) [Formula 8]. ). Embedded image Embedded image 7. A compound represented by the formula (VI)
I) a cross-linking group-containing molecular terminal represented by the following formula:
The cross-linking group-containing polyimide according to claim 6, wherein 95 to 1 mol% of the molecular terminals are molecular terminals that do not contain the cross-linking group represented by the formula (II) [Formula 9]. (VII) In the formula, Ar ₂ is a group represented by the formula (III)
It represents a divalent group selected from the group consisting of [Formula 9]. In the formula (III), R _{1 to} R ₆ may be each independently the same or different, and include —H, —F, a trifluoromethyl group, a methyl group, an ethyl group, Alternatively, it represents a phenyl group. In the formula (III) [Formula 9], Y is a group represented by the formula (I)
V) represents a trivalent group selected from the group consisting of [Formula 9]. In the formula (IV), Z is a direct bond,
_{O -, - SO 2 -,} - S -, - O -, - C (CH 3) 2 -, - C (C
And a divalent group selected from the group consisting of F ₃ ) _2- . ). Embedded image 8. The cross-linking group-containing polyimide according to claim 6, wherein the polyimide has a logarithmic viscosity represented by Formula (D) [Formula 4].
0.5 g of a crosslinking group-containing polyimide was added to a phenol / p-chlorophenol mixed solution (10 parts by weight / 90 parts by weight).
Logarithmic viscosity measured at 35 ° C. after dissolution at a concentration of / dl). [Equation 4] [η] = 0.2 to 2.0 dl / g (D) 9. A crosslinked polyimide obtained by heat-treating the crosslinked group-containing polyimide according to claim 6, wherein the crosslinked polyimide is a film (4 μm in thickness), and the film is a copper foil (18 μm in thickness). A cross-linked polyimide characterized in that the laminate does not peel and / or swell on the bonding surface after being immersed in a solder bath at 288 ° C. ± 5 ° C. for 10 seconds when the laminate is adhered to (1). 10. The crosslinked polyimide according to claim 9, wherein the heat treatment is a heat treatment at 250 to 450 ° C. for 0.1 second to 100 hours. 11. A heat-resistant adhesive comprising the polyimide according to claim 6. Description: